Method of manufacturing cellulose



Patented Oct. 24, 1933 UNITED, STATES METHOD OF MANUFACTURING CELLULOSE Joaquin Julio de la Bola, Sn, Tuinucu, Cuba No Drawing.

Application October 10, 1929 Serial No. 398,677

6 Claims. (01. 92-11) This invention relates to a method of manufacturing cellulose, and has for an object to provide for the production of soft, strong, fibrous material of very high alpha content, low ash content and exceptional quality, adapted. for use in various manufactures, the said material being produced from vegetable substances and more particularly from annual plants, such as the canes, corn stalks, straws and grasses, and 10 still more particularly from sugar cane fiber.

Another object consists in providing such a method whereby a fresh vegetable material, newly cut or harvested, may be given a first treatment, immediately thereafter stored, and then given two or more subsequent treatments leading to the desired product and avoiding deterioration or injury to the material.

Another object consists in providing such a method whereby such a vegetable material may be given a first treatment of an acid nature at substantially atmospheric pressure and temperature, then stored, then given another treatment of an acid nature at medium to high density and at temperature below'110 C., (preferably below 100 C.), then given one or more alkaline treatments suflicient to pulp the. material; the alkaline procedure being conducted either in one treatment at a temperature substantially above 100 C. or in two treatments, the first at approximately 100 C. and the second above Another object consists in providing such a method whereby the impregnation of the material withthe treating chemical is better accomplished, so that the uniformity and emciency of chemical action is promoted and a more complete charging of the treating vessels as we'll as economy of heating medium is attained.

Another object consists in providing such a method whereby treatments preliminary to the final pulping treatment afiect the material was to facilitate the subsequent recovery of chemicals employed and lower the non-cellulose constituents of the finished product.

'Another object consists in providing certain improvements in the method whereby advantageous results are attained.

This method is particularly applicable to, the manufacture of cellulose from sugar cane fiber, largely because that is an annual plant and the conditions attending sugar producion require a large portion of the fibrous material to be stored after it has been freshly cut from the growing state and before it can be fully processed and manufactured into cellulose; therefore I shall,

by way of setting forth the practical application of my invention, describe it in connection with the production of cellulose from sugar cane fiber.

It is my blief that I have devised a method of producing a very pure cellulose, which is 6 extraordinarily high in alpha content as well as in other distinctive characteristics of the best grade of this product; which method is commercially economical and practicable and does not impair the native strength-of the fibrous element of the vegetable substances, but obviates difliculties and disadvantages which have been prevalent in'connection with many prior methods, especially in respect to the treatment of annual plant fibers and, more especially, in

of my method, it may be noted that the manuv facture of sugar from cane is commonly accom-v panied by a treatment for the separation of the sugar juices from the fibrous part of the cane as,

for instance, by crushing between rollers or treatment in diffusers, and that this industry thus supplies a very large amount of fibrous material which is commonly very inefiicientlyemployed, if used at all. My method is thus adapted to the attainment of the'economic industrial achievement which resides in the utilization of this large amount of fibrous material in a commercially advantageous and highly remunerative manner.

Generally speaking, my method includes a first treatment with an acid solution for a considerable period of time at substantially atmospheric pressure and temperature; a second treatment at medium to high density with an acid solution conducted for a comparatively short period at below 110 C.; and either a third treatment at medium density with an alkaline solution of comparatively' low concentration conducted for a comparatively short period at substantially atmospheric pressure and at temperature below 0.; followed by a fourth treatment at high density with an alkaline. solution for a comparatively short period at elevated pressure and temperature; or a third and final treatment at me- Ell Sill

' ten squeezing on surplus liquid.

dlum density with an alkaline solution of medium concentration for a comparatively short period at elevated temperature and pressure.

The acid treatments are calculated to obviate various fungi and othergrowths that prey upon the encrustina' substances associated with the flben as well as partially to remove, or transform so as to nullify their injurious efiects, the sucrose, invert and other sugars, pentosans, and similar came-hydrates. together with coloring and mineral tters, etc. The first acid treatment not only renders the material suitable for storage without danger of deterioration or spontaneous injury, but it, together with the second acid treatment, partially or totally removes or nullifies these seriously objectionable substances which would not be satisfactorily removed by the eliteline treatments alone, and furthermore prepares the material ior satisfactory action by the subse uent treatments.

i find it desirable, between the acid and ultra lhie treatments, to wash the material (several times if practicable) preferably with hot water, although warm or cold water may he used with satisfactory results. This washing may be eiiectively carried out by supplying water tothe fiber and then straining and squeezing on the liquid by rollers or some other approved means. However, it may be conducted in any well known or approved manner as, ior instance, by repeatthe fiber in water, draining, and The washing step is calculated to remove quantities oi these substances which are in condition for solution or separation by the water at that stage of the method.

treatment, and it serves to pulp the material and adapt it for the final customary steps in the manuiacture of cellulose, lead to the product with minimum loss of strength, maxim yield, light color, low ash, and high purity.

ln folio a. the prcierred mer of car out invention, the sugar cane fiber obtained from the crushing rollers or. diffusers, which should be as tree as his irom or, is weighed and thereafter conveyed by a belt, or other suitable contrlvance. toapparatus. such as shredding and screening devices. tor the i oi tear. the fiber bunes a and separating the dust lilre or short'oud fibrous material, commanly known as pith,- for stroncer fibrous material to portions oi the cane. The longer and stronger I fibers are then treated preferably with a dilute may be conveniently accomplished by thoroughly spra the solution from beneath the material as it is being carried from the shredding and devices to storage, care being taken to avoid too time a spray which might tend to form sulphuric acid or to cause loss oi too much sulphur dioxide to the air. If the storage is under such "conditions as to allow any substantial evaporation or loss of solution, it is advisable occasionally to add to the material more or the solution of sulbe, and frequently is, for a period of seve months.

Another way of accomplishing this treatment is to entirely immerse the material in the sul-' phurous acid solution or solution of sulphur dioxide and water contained in suitable vats or the like protected against the action of the acid, and to permit the material thus to remain d the period of storage or treatment. Or the terial may be sprayed and then ersed in the solution. I

It will be understood that this treatment at: be carried out in other ways and it should be noted that, in any case, I prefer to conduct this treatment at substantially atmospheric pree and temperature. if conditions should require, suitable temperature controlling apparatus may be employed to maintain. the temperature at substantially the normal atmospheric temperature of sugar cane growing localities but, ordinarily, in the tropics this will not be necessary. it should further be noted that the object oi this sul phurous acid treatment is not to pulp the lllltllt rial, but is rather to lead to the protection of the fibrous cellulosic material while in storage and to the separation of certain substances as hereinabove indicated.

The period during which the material remains in storage subject to this acid treatment may, oi course, vary; but usually it will be a tter of l mo several months, or from crop to crop. Iii the material hasbeen immersed in the acid solution, it may suitably be removed therefrom tor the following step by bucket cranes or the like haviin those parts designed to enter the solution pro= llil tested against the action oi the acid.

The: second acid treatment is preferably p formed by heating the fibrous terial in a closed vessel with a solution of sulphur dioxide in water and containing, for instance, about twelve to lid twenty five or thirty pounds of sulphur dioxide for each one hundred pounds oi ne dry fiber in the charge, to a temperature not to'erceed C. I have obtained good results at about 98 C. Jllthough, at this temperature of as" ((3., ltd the solution will not be boiling, the formation of sulphur dioxide gas calls for the use of a closed vessel. While a standard sulphite diuester de signed for much lower pressure than customary mil for the U. S. patent application, derial No. nacic. filed December 1d, 1929.

The material is introduced into the vessel for this acid treatment preferably at high an rec that is. fifty or more percent oi the to weight may be dry fiber. The acid solution is then added and it is ediately heated, as by an or with ste coils. until a perature of not more-than 110 C. is reached in about one hour. A temperature of about 98 C. is preferred, but a temperature of 90 C. also gives good results although requiring more time. The charge is kept at this temperature for. a period of time, depending on the quality of product desired, but too preferably three ormore hours. Naturally a longer time will have a more complete eficct, but this will tend to reduce the capacity of the plant. and, it continued too long, may injure the fiber, so that the time should be proportioned to the quality of product desired. A few minutes give a good quality of cellulose for paper, whereas, for the production of high alpha cellulose, the full time of three or more hours is required. Such treatment with acid solution is very let partially removes or transforms other substancesso that they may be readily removed by the subsequent treatments.

At the end of the selected period, the gas is first released to be recovered in the usual manner and the material is washed with'water and removed from the vessel for squeezing and washing which may be conducted in any suitable apparatus; further recovery of gas being obtained from the various acid liquors. The surplus li uid is eliminated by pressure or the like, leaving the material comparatively free from acid and concentrated to from fifteen to-i'ifty percent of dry fiber depending on the pressure applied. Hot, warm or cold water may be used for washing, it being understood that hot water is generally to be preferred and that the more water used the more thorough the washing and the more improved the quality of the product.

The acid solutions employed in the first two treatments should be devoid of any added or combined base, it being understood that the presence of such base or bases is detrimental to the best quality of product, in proportion to the quantity of base employed;

In case it is not desired to store the material before complete processing, or if it should be preferred for any other reason, the acid pro cedure may be performed in a single treatment instead 0! in two treatments, which single treatment substantially combines the intensity of the the acid treatment may be conducted in a closed vessel as explained in connection with the above described second treatment, except that the solution of sulphur dioxide should be of a strength equal to about sixteen to thirty or thirty-five pounds of sulphur dioxide for each one hundred pounds oi bone dry fiber in the charge; and the period of time should ordinarily be about six or seven hours, at the stated temperature of less than llil 6., and preferably at approximately 98 C. This procedure is somewhat simpler than the two treatment procedure but it is not feasible where storage of the material for any extended period prior to manufacturing the cellulose therefrom is necessary.

It should be noted that, whether the acid procedure embodies the two treatments or the single treatment, it involves the application of a concentrated acid solution as distinguished from a very dilute solution; but, in either case also, the acid procedure is not calculated to or sufllcient to pulp the material but is only adequate to accomplish the purposes hereiuabove recited. The use of a concentrated acid solution as distinguished from a dilute acid solution does not serve merely to reduce the time and/ or temperature factors required toattain a given result. It has a distinct eil'ect upon the product with respect to the matter oi alpha cellulose content. In other words, treatment with a concentrated solution enables the gttgielll; of a very high alpha cellulose which could not be approximated by using a dilute solulow 100 C. and at substantially atmospheric pressure, preferably in a vessel suitably protected from corrosion. For the purpose of this treatment any suitable alkali may be used, depending upon the quality of product desired, although generally it is better to employ an alkali having a sodium etc. Likewise, alkaline with sodium hydroxide, or sodium sulphite, or-

other alkalies, all depending on the cost and the results desired. In general it may be stated that it is desired to employ in this treatment an alkali having a strength equivalent to from two to fourteen percent sodium hydroxide based on the bone dry weight of fiber, either as sodium hydroxide alone or as a mixture of one or more alkalies; or, in other words, equivalent to two to fourteen pounds sodium hydroxide for each one hundred pounds of bone dry fiber. p

In cases where an expensive alkali is necessitated by the higher quality of product desired, at least a portion of the chemicals may be recovered by the usual processes of evaporating the used liquors, concentrating and burning to powder containing the larger portion of the base (usually sodium) and regenerating the alkali from such base. Sodium sulphide alone is quite satisfactory for use in this treatment but, owing to the production of sodium hydroxide in the customary recovery processes and dimculties in recovering the sodium base that is combined with certain substances,: there naturally is employed a mixture or sodium sulphide and sodium hydroxide when so dium sulphide is used. Practice has demonstrated that, where a high alpha product is required, the use or sodi or potassium hydroxide is indicated.

In preparing this aqueous alkaline solution, it is economical and practical to employ a substan tial amount of the weaker so called black liquor the eliminating action of the previous treatments,

that an exceptionally large amount oi the said black liquor may be employed in prep the alkaline solutions. This efiects a great economy and is of prime consequence in relation to a profitable commercial operation.

This alkaline solution is preferably added to the fiber by mixing in a vat or the like provided with agitating devices, such as paddles, in order that the fiber may be thoroughly impregnated with thesolution. Following such mixing, the material may be pumped or it may flow by grayity, or it may be conveyed, to the nest operation where the excess liquid may he removed by pres sure and screening apparatus oi any well known and approved form, leaving the fiber thoroughly saturated with the alkaline solution. This procedure is of substantial advantage beceuse it eliminates the injection or ecessaiy liuuid intothe vessel designed for the said treatment and thereby increases the amount of fiber included in any given charge of said vessel,.and also provides for more even cooking, by properly g and distributing the alkali with and through the fiber.

The vessel in which this alkaline treatment is carried out may be provided with temperature controlling appliances or the charge may be directly heated by the injection of steam, and I profear to carry out this treatment at a temperature which is slightly less than 100 C., and at sub- I the high pr ment have been hereinbefore explained, it is un- Ma: -1 to repeat at this juncture; but I may main call attention to the mild strength of chemical employed and to the low temperature and premure.

[it the end of this alkaline treatment, the excess liquid is removed from the fiber as, for instance, by diluting, screening and pressing api paratus, which excess liquid carries on with it most of the objectionable substances previously stawd as being a 1. inated by this treatment, and the material may then be washed, if desired, to promote whi.

The l treatment, M already noted, is of an alkaline nature, but it is conducted at elevat ed pressure and temperature, though preferably not above ldil C. lit the outset of this treatment, the fiber is again mixed with an alkaline solution, preferably oi the character above de so that the fiber may be thoroughly permooted by and impregnated with the alkaline solution. The strength of this solution may vary rudder dhterent clrciunstances, but I prefer to use one oi about four to eleht percent alkali based on. the bone dry weight of the bloom; t is to say, four to eight pounds of sodium hydroiddefor every one hundred pounds of bone fiber. Edie thorough impregnation of the fibrous mate= rial by the alkali in connection with this allraline treatment is oi even more portance than in connection with the previous treatment because, among other reasons. it is of more eco= nonric valuev fully to charge the digesters used in p e treatment than the vats used in the low pressure treatment, and also because the complete saturation of the fiber with the alhaline solution protects it against injury upon the application or heat for generating the high temperature employed, which heat might tend eerie to injure any part of the fiber that had not been reached by the 11. Again, this thor- @mh a: 4:1: es uniform distribution of the chcal which entails uniform action.

t eel for menses protected, in any well known or approved man-- ner, against the chemical action involved. The arrangement of valves, vents, and the like, may difier to a certain extent from the standard arrangement of the sulphite digesters, but such changes are well within the skill of the calling and merely for the purpose of better adapting the apparatus to the specific conditions in hand. It should be stated,-however, that the said fittings should be protected against the chemical action of the treatment. After the charge has been passed into this vessel, the valves, vents, and the like, are closed, and the same is heated indirectly or directly by steam until a temperature of approximately 140 c.-1co C. has been reached and a correspoding pressure generated. The charge is then maintained at substantially this temperature and pressure for about four to six or more hours, which period of time may, of course, be varied in compliance with different circumstances.

After this period has expired, the fibrous ma terialmay be removed from the digester, as by blowing into a pit or other container, and thereafter washed in a suitable manner with water, bleached and otherwise finally treated, all as is well understood in this art. It may be said that, for certain purposes, the bleaching may be climbnated because the unbleached product is very light in color, but, if an absolutely pure white product is desired, there should be some bleaching. The cellulose product will be found to have all the high quality s hereinbelore recited. Where sulphate liquor is .sed in the alkaline steps the product will have more nearly the strength oikrait and yet will be white, so that I have termed such product white lsraft. It should be pointed out as a characteristic oi this procedure that no one of the treatments de-. scribed is, of itself, adequate to produce a fully pulped fiber. True, the final treatment accomplishes this pulping, but that is because of the efiect of the preceding treatments which have so acted upon the fibrous material as to render it susceptible to pulping by the final alkaline treatlid lid

ment, which treatment is of such a mild nature that it would not, on? itself, pulp the fibrous material if it had not been subject to the earlier treatments of the method.

it desired, the alkaline procedure may be con-.- ducted in one treatment instead of two, in which case I prefer to use a solution having a strength equivalent to twelve to twenty-five ,or more pounds of sodium hydroxide per one hundred pounds of bone fiber; to use a temperature oi C. to 16W 0.: and to conduct the treatment tor a period of tour to six hours or more.

The temperature may be less than 140 C. if the period of time is appropriately extended. This single alkaline treatment is naturally simpler than the double treatment, but the latter preferred when a product of very high alpha.-

content is demanded.

Although I have described above the separation of the lo fibers and their treatment, the method is also applicable to the treatment ofthe whole of the fiber without such separation and,

further, the separation may take place and the short fibers be treated instead of the long.

Again, while I have described the treatment of sugar cane fiber resulting from cane which has been put through the usual processes for extracting the sugar, it is an advantage of this invention that I may utilize fiber obtained from sugar cane which has been damaged with respect to its adaptibility for the manufacture of sugar as, for instance, by fires in the field. Such damaged sugar cane, even though it may be unsuitable for the production of sugar, includes fibrous material which is well adapted for treatment by my above described method whereby the uniniured fibers can be separated and the intended product obtained. Furthermore, as

above indicated,'this method is adapted to the' treatment of other vegetable substances contain-.

ing cellulose fibers so that when, in the claims, I refer to vegetable fiber, I intend to cover the treatment of such fiber in any form or condition suitable to the application of my method. Finally,

when I refer to acid and alkali, I intend to cover not only those specifically'named, but also others having a similar effect in my method, though for acid I prefer .a solution of sulphur dioxide and water without any added or combined base, and for alkali I prefer sodium or potassium hydroxide.

In the foregoing I have referred to apparatus in general terms without herein presenting any claims to apparatus, and I should say that this failure further to describe and claim any such apparatus is not to be regarded as a dedication of the same.

In connection with the alkaline treatment I have suggested the premixing of the chemical with the fiber and the removal of the excess chemical before initiating the treatments, and have pointed out certain advantages that'reside in this procedure. It may here be added that the said premixing and removal of excess chemical may also be advantageously adopted in connection with the acid treatment, where the strength of acid used and temperature are low.

It will be understood that various changes may be resorted to in the steps of the method, in the materials and in the apparatus, without departing from the spirit and scope of my invention; and hence I do not intend to be limited to the details herein set forth, except as-they may be included in the claims.

What I claim is:

1. A method of treating vegetable fiber to pro.- duce cellulose of very hgh alpha content, low ash content and exceptional quality, which includes, treating the fiber with a concentrated solution of sulphur dioxide and water containing at least twelve pounds of sulphur dioxide for each one hundred pounds of bone dry fiber and,

. subsequently, treating the fiber with alkali.

2. A method of treating vegetable fiber to produce cellulose of very high alpha content, low ash content and exceptional quality, which in-- cludes, treating the fiber with a concentrated solution of sulphur dioxide and water containing at least twelve pounds of sulphur dioxide for each one hundred pounds of bone dry fiber, washing .the fiber and, subsequently, treating the fiber with alkali.

3. A method of treating vegetable fiber to produce cellulose of very high alpha content, low ash content and exceptional quality, which includes, treating the fiber with a solution of sulphur-diox'de and water, storing the fiber, again treating the fiber with a solution of sulphur dioxide and water and, subsequently, treating the fiber with an alkaline solution.

4. A method of treating vegetable fiber to produce cellulose of very high alpha content, low ash content and exceptional quality, which includes, treating the fiber with a solution of sulphur dioxide and water, storing the fiber. again treating the fiber with a solution of sulphur dioxide and water and, subsequently, treating the fiber with a plurality of alkaline solutions.

5. A method of treating vegetable fiber to pro-' duce cellulose of very high alpha content, low ash content and exceptional -quality, which includes, treating the fiber with a solution of sulphur doxide and water, storing the fiber, again treating the fiber with a solution of sulphur dioxide and water and, subsequently, treating the fiber with a plurality of alkaline solutions, said acid treatments being of increasing intensity and said alkaline treatments being of increasing intensity.

6. A method of treating vegetable fiber to produce cellulose of very high alpha content, low ash content and exceptional quality, which in cludes, treating the fiber with a solution of sulphur dioxide and water, storingthe fiber, again treating the fiber with a solution of sulphur dioxide and water and, subsequently, treating the fiber with a plurality of alkaline solutions, said acid treatments being conducted at temperatures below 110 0., an alkaline treatment being conducted at substantially atmospheric pressure and at temperature below boiling, and another alkaline treatment being conducted at pressure above 1 

